CN104334602A - Liquid hardeners for hardening epoxide resins (I) - Google Patents
Liquid hardeners for hardening epoxide resins (I) Download PDFInfo
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- CN104334602A CN104334602A CN201380029718.7A CN201380029718A CN104334602A CN 104334602 A CN104334602 A CN 104334602A CN 201380029718 A CN201380029718 A CN 201380029718A CN 104334602 A CN104334602 A CN 104334602A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
The present invention relates to novel latent hardeners for hardening hardenable polymer resins, particularly epoxide resins, and epoxide resin compositions and to use thereof for producing composite fibre materials.
Description
The present invention relates to for curable polymeric resin, the new liquid solidifying agent of the particularly solidification of epoxy resin, and comprise the epoxy resin-composition for the preparation of fibre composite of described solidifying agent.
Due to the chemical resistant properties that thermosetting epoxy resin is good, fabulous thermal characteristics and dynamic properties and high electrical isolation capabilities thereof, thermosetting epoxy resin is widely used.In addition, epoxy resin demonstrates good adhesion and is therefore particularly suitable for being used in fibre composite (mixture) on many base materials.In order to be used in fibre composite, well moistening (namely for the preparation of the low viscosity of the resin formulations selected by matrix material) of fiber and high mechanical property are after solidification desirable.
In order to be prepared into shaped piece by fibre composite, use diverse ways, such as preimpregnation method, different method for filling or injecting method, particularly RTM-method (resin transfer molding).In these methods, particularly method for filling or injecting method are significant in the past few years.Therefore such as in method for filling, be wherein arranged in the dry reinforcement material of chunk, such as fiber mat, non-woven fabric, fabric or knitted fabrics, covered by sealed vacuum film and flooded by divider passage resin formulations after applying vacuum.The advantage of described method is, can within a short period of time the shaping Large components with complex geometric shapes.
Epoxy resin formulations for method for filling or injecting method must have low viscosity, thus can impregnated fiber material within the corresponding time in a vacuum.When use there is the resin formulations of too high viscosity time or when being used in injection during, during the resin formulations of too fast formation too high viscosity, in produced mixture, obtain non-impregnation section and other defect sites.
The solidification of epoxy resin is carried out according to different mechanism.Except with except phenol or anhydride-cured, be usually cured with amine.These materials are generally liquid and can mix admirably with epoxy resin.Due to high reactivity and therefore extremely low latent (Latenz), this composition epoxy resin is prepared with the form of two component.This means resin (A-component) and solidifying agent (B-component) separately stores and just mixes with correct proportions before the use.In this article, " latent " means mixture stable existence under the condition of storage limited of each component.Two components resin preparaton is also referred to as so-called cold-set resin preparaton, and the solidifying agent wherein for this reason used is selected from amine or amido amine usually.
On the contrary, single-component thermosetting epoxy resin formulations is produced in advance with operational form, that is epoxy resin and solidifying agent exist with the form mixed by manufacturer.Therefore the mixing mistake of each component when using at the scene is eliminated.Latent curing agent system forms its prerequisite, and described latent curing agent does not at room temperature react with epoxy resin (can store), but is easy to reaction when heating according to energy input.For described single component epoxy-preparaton, such as Dyhard RU 100 is suitable especially and the solidifying agent of cost advantages.At ambient conditions, corresponding resin-hardener-mixture can be stored to many ten two (12) individual months with operational form.
The shortcoming that the epoxy resin composition regrettably with high latent Dyhard RU 100 or other high latent curing agent has is, solidifying agent is difficult to dissolve in the epoxy and is caught by fiber mat at the entry site place of resin in for the preparation of the method for filling of fibre composite or injecting method and leach.Therefore solidifying agent cannot be mixed in the resin of mixture equably before application.Therefore the solidification of whole mixture is hindered.
In the patent literature description is rarely had to the proposal for overcoming these shortcomings.German patent application DE 27 43 015 A1 and austrian patent AT 351 772 describes separately by using the cyanamide mixture or the aqueous solution of cyanamide thus the method for cured epoxy resin with 75 % by weight ureas at the most.Also can be cured by using the promotor of catalytic amount.Epoxy resin-the composition of corresponding preparation may be used for the glasscloth preparing preimpregnation, so-called preimpregnation material.Therefore these two sections of patent documentations describe the liquid curing-agent aqueous solution.But its shortcoming is, described solidifying agent is solution, must remove its aqueous solvent in the curing process, thus the Quality Down through being solidified into shaped piece do not caused.The selection of described shortcoming and solvent has nothing to do, because must remove desolventizing all the time in the curing process.
In addition, undocumented patent application PCT/EP2012/053092 and PCT/EP2012/053091 describes the liquid curing-agent of the solidification for curable polymeric resin, and described solidifying agent comprises cyanamide and at least one to the urea derivatives of fixed pattern.
The object of the invention is to, be provided for curable polymeric resin, the Novel curing agent of the particularly solidification of curable epoxy, and epoxy resin-composition, described epoxy resin-composition may be used for preparing mixture and fibre-reinforced matrix.In addition, described solidifying agent also needs the advantage in conjunction with known amine hardener and known Dyhard RU 100 powder curing agent and does not have its shortcoming, the such as filtration of low latent or particle.Described Novel curing agent should have high latent and therefore have the high storage stability under solidification value and the hyperergy under solidification value, epoxy resin can be made completely crosslinked, epoxy resin can be dissolved in or can mix completely with epoxy resin and be suitable for method for filling, injecting method or RTM-method.
Described object is realized by liquid curing-agent according to claim 1.Therefore according to first embodiment, theme of the present invention is for fluoropolymer resin, particularly curable polymeric resin, the particularly liquid curing-agent of the solidification of curable epoxy, urethane resin and composition thereof, described solidifying agent comprises a) cyanamide, b) urea derivatives of at least one formula (I), and c) at least one viscosity modifier, described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, polyether glycol, ketone, aldehyde, nitrile, carboxylicesters or its mixture, and wherein urea derivatives has following structure
Formula (I)
Wherein group meets as follows and at least one radicals R simultaneously or independently of one another
1, R
2, R
3be not hydrogen:
R
1, R
2=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C10-alkylidene group by forming ring;
R
3=hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, aryl, aralkyl, use-NHC (O) NR
1r
2c1-to the C15-alkyl, use-NHC (O) NR that replace
1r
2c3-to the C15-cycloalkyl, use-NHC (O) NR that replace
1r
2the aryl replaced, or with-NHC (O) NR
1r
2the aralkyl replaced.
According to the present invention importantly, liquid curing-agent according to the present invention comprises cyanamide (CAS420-04-2).Have been surprisingly found that, cyanamide and at least one according to have above-mentioned implication formula (I) urea derivatives be closely mixed to form there is low melting point (compared to initial substance) liquid to semiliquid mixture, described mixture is at room temperature dissolved in epoxy resin completely or mixes completely with epoxy resin.Although there is the material of separation analytically as beforely, DSC-analyzes the endothermic melting peak showing single substance system.Described mixture can mix and its liquid state of not remarkably influenced with viscosity modifier, described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, ether alcohol, polyether glycol, ketone, aldehyde, nitrile, carboxylicesters or its mixture, and described mixture is suitable for fluoropolymer resin with flying colors, the solidification of particularly curable polymeric resin, particularly curable epoxy, curable polyurethane resin or its mixture.Its mode of action is in the epoxy suitable with the curing performance of the Dyhard RU 100 accelerated with imidazoles and be <100 DEG C.However, the latent of a couple of days to several weeks is at room temperature still obtained.
Also have been surprisingly found that, compared to powdered mixture or the suspensoid with same composition, according to the solidification of liquid curing-agent of the present invention initiated polymerization resin at lower temperatures all the time, therefore can realize the shorter time for the preparation of profiled member.
In addition can by liquid resin remarkably influenced according to the present invention complete through preparation resin, the particularly viscosity of epoxy resin-composition, therefore described solidifying agent is suitable for use in perfusion resin or with flying colors for the preparation of in the resin of preimpregnation material, particularly because achieve the significant saving of time for the preparation of profiled member.Can such as use viscosity modifier for the preparation of preimpregnation material, described viscosity modifier causes the viscosity of gained resin-composition to raise.Therefore the adhesion good especially on a support material of gained resin-composition is realized.On the other hand, the viscosity of resin-composition to be prepared can be reduced by adding suitable viscosity modifier, wherein in liquid curing-agent according to the present invention, adding corresponding viscosity modifier.This liquid curing-agent with viscosity lowering energy can be used in method for filling or injecting method especially well.Viscosity modifier can be added in liquid curing-agent according to the present invention, and its liquid state of not remarkably influenced.Special surprisingly, properties-correcting agent negative impact can not add the latent of the resin-composition of liquid resin in many cases.Also find on the contrary, latent can raise and therefore the storage power of gained resin-composition can be improved.
It is emphasized that the drawbacks common not observing other liquid curing-agent, such as extremely low latent and therefore at room temperature high reactivity.The resin with the second-order transition temperature higher compared to the resin solidified with amine hardener solidified with solidifying agent according to the present invention can also be provided.
Therefore can provide liquid curing-agent in a word, described solidifying agent due to the high latent in fluoropolymer resin-composition and in fluoropolymer resin-composition hyperergy at curing temperatures and being suitable for use in flying colors in method for filling or injecting method.
Can design so in embodiments of the invention, liquid curing-agent is with the cyanamide of 1:1 to 4:1: the molar ratio of urea derivatives or urea derivatives mixture comprises the urea derivatives of cyanamide and at least one formula (I) or the mixture of described urea derivatives.Especially, design like this according to the present invention, cyanamide: the molar ratio of urea derivatives or urea derivatives mixture is 1:1 to 3:1, more preferably 1:1 to 2:1, and very preferably 2:1 to 4:1.
Under the existence of at least one viscosity modifier, described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, ether alcohol, polyether glycol, ketone, aldehyde, nitrile, carboxylicesters or its mixture, cyanamide: the molar ratio of urea derivatives also can drop on outside the preferable range of 1:1 to 4:1.Such as, 0.1 to <1:1, the particularly cyanamide of 0.2 to <1:1: the molar ratio of urea derivatives is possible, the cyanamide of >4:1 to 20:1, particularly >4:1 to 10:1: the molar ratio of urea derivatives is also possible.
According to the present invention, liquid curing-agent is appreciated that its fusing point S
mfor S
m<20 DEG C (standard atmosphere pressure) or exist in liquid form at the temperature of 20 DEG C (standard atmosphere pressures) and there is the solidifying agent of the viscosity being less than 1Pa*s.According to liquid curing-agent of the present invention, preferably there is at 25 DEG C≤100mPa*s, more preferably <20mPa*s, the viscosity of also more preferably≤12mPa*s.But particularly preferably such liquid curing-agent, described solidifying agent has S
mthe fusing point S of <10 DEG C (standard atmosphere pressure)
m, very particularly preferably S
mthe fusing point S of <0 DEG C (standard atmosphere pressure)
m, or at the temperature of 10 DEG C (standard atmosphere pressure), very particularly preferably at the temperature of 0 DEG C, (standard atmosphere pressure) exists in liquid form and has the viscosity being less than 1Pa*s.
It is emphasized that described solidifying agent this as liquid and especially except cyanamide, comprise at least one urea derivatives or its mixture and at least one containing the viscosity modifier of solvent or solubilizing agent, therefore containing solvent or not containing solubilizing agent.For the present invention, for the preparation of the inorganic of solvent or organic solvent or solubilizing agent or its mixture when solvent or solubilizing agent are understood to be in chemosynthesis separately or analyze.But according to viscosity modifier of the present invention not containing solvent.For the present invention, containing solvent or containing solubilizing agent be understood to be substantially free of solvent or solubilizing agent and affect by preparation and comprise the highest solvent of 1.0 % by weight or the solidifying agent of solubilizing agent.
But in a substituting embodiment also possible that, solidifying agent comprises solvent, particularly water.In order to make mixture become liquid, adding of solvent is unnecessary, but requires it may is useful for other method.
In addition, about the present invention, C1-to C15-alkyl is appreciated that chain length is the linear of 15 carbon atoms at the most or branched-alkyl, and it has general formula C especially
nh
2n+1, wherein n=1 to 15.Preferably design like this, C1-to C15-alkyl can represent methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl, and wherein these alkyl can be preferably also nonbranched, single branching, hyper-branched or alkyl replacement.
Preferably such C1-to C15-alkyl, described C1-to C15-alkyl itself carries out monosubstituted or polysubstituted, particularly replaces with C1-to C5-alkyl.Methyl, ethyl, n-propyl, 1-methylethyl, normal-butyl, 1-methyl-propyl, 2-methyl-propyl, 1 can be preferably represented further according to C1-to C5-alkyl of the present invention, 1-dimethyl ethyl, n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 2,2-dimethyl propyls or 1-ethyl propyl.Therefore C1-to C15-alkyl according to the present invention can also represent 1-methylethyl especially, 1-methyl-propyl, 1-methyl butyl, 1-methyl amyl, 1-methylhexyl, 1-methylheptyl, 1-Methyl Octyl, 1-Nonyl, 1-methyldecyl, 1-ethyl propyl, 1-ethyl-butyl, 1-ethyl pentyl group, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctanyl, 1-ethylnonanyl, 1-ethyl decyl, 2-methyl-propyl, 2-methyl butyl, 2-methyl amyl, 2-methylhexyl, 2-methylheptyl, 2-Methyl Octyl, 2-Nonyl, 2-methyldecyl, 2-ethyl propyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethylheptyl, 2-ethyloctanyl, 2-ethylnonanyl, 2-ethyl decyl, 1,1-dimethyl ethyl, 1,1-dimethyl propyl, 1,1-dimethylbutyl, 1,1-dimethyl amyl group, 1,1-dimethylhexanyl, 1,1-dimethyl heptyl, 1,1-dimethyl octyl group, 1,1-dimethyl nonyl, 1,1-dimethyl decyl, 1,2-dimethyl propyl, 1,2-dimethylbutyl, 1,2-dimethyl amyl group, 1,2-dimethylhexanyl, 1,2-dimethyl heptyl, 1,2-dimethyl octyl group, 1,2-dimethyl nonyl, 1,2-dimethyl decyl, 2-ethyl-1-methyl butyl, 2-ethyl-1-methyl amyl, 2-ethyl-1-methylhexyl, 2-ethyl-1-methylheptyl, 2-ethyl-1-Methyl Octyl, 2-ethyl-1-Nonyl, 2-ethyl-1-methyldecyl, 1-Ethyl-2-Methyl propyl group, 1-Ethyl-2-Methyl butyl, 1-Ethyl-2-Methyl amyl group, 1-Ethyl-2-Methyl hexyl, 1-Ethyl-2-Methyl heptyl, 1-Ethyl-2-Methyl octyl group, 1-Ethyl-2-Methyl nonyl or 1-Ethyl-2-Methyl decyl.
Also preferably, C1-to C15-alkyl (particularly methyl, ethyl, propyl group, butyl) itself can also by C3-to C15-cycloalkyl substituted, and wherein C3-to C15-cycloalkyl has implication described below.Therefore C1-to C15-alkyl can also represent C3-to C15-cycloalkylmethyl, 1-(C3-to C15-cycloalkyl)-1-ethyl, 2-(C3-to C15-cycloalkyl)-1-ethyl, 1-(C3-to C15-cycloalkyl)-1-propyl group, 2-(C3-to C15-cycloalkyl)-1-propyl group or 3-(C3-to C15-cycloalkyl)-1-propyl group especially, and wherein C3-to C15-cycloalkyl has implication described below.
About the present invention, C3-to C15-cycloalkyl is appreciated that the monocycle or bicyclic cycloalkyl with 3 to 15 carbon atoms, particularly has general formula C
nh
2n-1cycloalkyl, wherein n=3 to 15.Also preferably, C3-to C15-cycloalkyl can representative ring propyl group, cyclobutyl, cyclopentyl, cyclohexyl or suberyl, and wherein these cycloalkyl itself also preferably can be carried out monosubstituted or polysubstituted with C1-to the C5-alkyl with above-mentioned implication.Also preferably, therefore C3-to C15-cycloalkyl can also represent 1-methyl isophthalic acid-cyclopropyl, 1-methyl isophthalic acid-cyclobutyl, 1-methyl isophthalic acid-cyclopentyl, 1-methyl isophthalic acid-cyclohexyl, 1-methyl isophthalic acid-suberyl, 2-methyl isophthalic acid-cyclopropyl, 2-methyl isophthalic acid-cyclobutyl, 2-methyl isophthalic acid-cyclopentyl, 2-methyl isophthalic acid-cyclohexyl, 2-methyl isophthalic acid-suberyl, 3-methyl isophthalic acid-cyclobutyl, 3-methyl isophthalic acid-cyclopentyl, 3-methyl isophthalic acid-cyclohexyl, 3-methyl isophthalic acid-suberyl, 4-methyl isophthalic acid-cyclohexyl, 4-methyl isophthalic acid-suberyl, 1,2-dimethyl-1-cyclopropyl, 2,2-dimethyl-1-cyclopropyl, 2,3-dimethyl-1-cyclopropyl, 1,2-dimethyl-1-cyclobutyl, 1,3-dimethyl-1-cyclobutyl, 2,2-dimethyl-1-cyclobutyl, 2,3-dimethyl-1-cyclobutyl, 2,4-dimethyl-1-cyclobutyl, 3,3-dimethyl-1-cyclobutyl, 1,2-dimethyl-1-cyclopentyl, 1,3-dimethyl-1-cyclopentyl, 2,2-dimethyl-1-cyclopentyl, 2,3-dimethyl-1-cyclopentyl, 2,4-dimethyl-1-cyclopentyl, 2,5-dimethyl-1-cyclopentyl, 3,3-dimethyl-1-cyclopentyl, 3,4-dimethyl-1-cyclopentyl, 1,2-dimethyl-1-cyclohexyl, 1,3-dimethyl-1-cyclohexyl, Isosorbide-5-Nitrae-dimethyl-1-cyclohexyl, 1,5-dimethyl-1-cyclohexyl, 1,6-dimethyl-1-cyclohexyl, 2,2-dimethyl-1-cyclohexyl, 2,3-dimethyl-1-cyclohexyl, 2,4-dimethyl-1-cyclohexyl, 2,5-dimethyl-1-cyclohexyl, 2,6-dimethyl-1-cyclohexyl, 3,3-dimethyl-1-cyclohexyl, 3,4-dimethyl-1-cyclohexyl, 3,5-dimethyl-1-cyclohexyl, 3,6-dimethyl-1-cyclohexyl, 4,4-dimethyl-1-cyclohexyl, 1,2,2-trimethylammonium-1-cyclopropyl, 1,2,3-trimethylammonium-1-cyclopropyl, 1,2,2-trimethylammonium-1-cyclobutyl, 1,3,3-trimethylammonium-1-cyclobutyl, 1,2,3-trimethylammonium-1-cyclobutyl, 2,2,3-trimethylammonium-1-cyclobutyl, 2,2,4-trimethylammonium-1-cyclobutyl, 1,2,2-trimethylammonium-1-cyclopentyl, 1,2,3-trimethylammonium-1-cyclopentyl, 1,2,4-trimethylammonium-1-cyclopentyl, 1,2,5-trimethylammonium-1-cyclopentyl, 1,3,3-trimethylammonium-1-cyclopentyl, 1,3,4-trimethylammonium-1-cyclopentyl, 1,3,5-trimethylammonium-1-cyclopentyl, 2,2,3-trimethylammonium-1-cyclopentyl, 2,2,4-trimethylammonium-1-cyclopentyl, 2,2,5-trimethylammonium-1-cyclopentyl, 2,3,3-trimethylammonium-1-cyclopentyl, 2,3,4-trimethylammonium-1-cyclopentyl, 2,3,5-trimethylammonium-1-cyclopentyl, 2,3,3-trimethylammonium-1-cyclopentyl, 2,4,4-trimethylammonium-1-cyclopentyl, 2,4,5-trimethylammonium-1-cyclopentyl, 2,5,5-trimethylammonium-1-cyclopentyl, 3,3,4-trimethylammonium-1-cyclopentyl, 3,3,5-trimethylammonium-1-cyclopentyl, 3,4,5-trimethylammonium-1-cyclopentyl, 3,4,4-trimethylammonium-1-cyclopentyl, 1,2,2-trimethylammonium-1-cyclohexyl, 1,2,3-trimethylammonium-1-cyclohexyl, 1,2,4-trimethylammonium-1-cyclohexyl, 1,2,5-trimethylammonium-1-cyclohexyl, 1,2,6-trimethylammonium-1-cyclohexyl, 1,3,3-trimethylammonium-1-cyclohexyl, 1,3,4-trimethylammonium-1-cyclohexyl, 1,3,5-trimethylammonium-1-cyclohexyl, 1,3,6-trimethylammonium-1-cyclohexyl, Isosorbide-5-Nitrae, 4-trimethylammonium-1-cyclohexyl, 2,2,3-trimethylammonium-1-cyclohexyl, 2,2,4-trimethylammonium-1-cyclohexyl, 2,2,5-trimethylammonium-1-cyclohexyl, 2,2,6-trimethylammonium-1-cyclohexyl, 2,3,3-trimethylammonium-1-cyclohexyl, 2,3,4-trimethylammonium-1-cyclohexyl, 2,3,5-trimethylammonium-1-cyclohexyl, 2,3,6-trimethylammonium-1-cyclohexyl, 2,4,4-trimethylammonium-1-cyclohexyl, 2,4,5-trimethylammonium-1-cyclohexyl, 2,4,6-trimethylammonium-1-cyclohexyl, 2,5,5-trimethylammonium-1-cyclohexyl, 2,5,6-trimethylammonium-1-cyclohexyl, 2,6,6-trimethylammonium-1-cyclohexyl, 3,3,4-trimethylammonium-1-cyclohexyl, 3,3,5-trimethylammonium-1-cyclohexyl, 3,3,6-trimethylammonium-1-cyclohexyl, 3,4,4-trimethylammonium-1-cyclohexyl, 3,4,5-trimethylammonium-1-cyclohexyl, 3,4,6-trimethylammonium-1-cyclohexyl, 3,5,6-trimethylammonium-1-cyclohexyl, 1,2,3,3-tetramethyl--1-cyclopropyl, 2,2,3,3-tetramethyl--1-cyclopropyl, 1,2,2,3-tetramethyl--1-cyclopropyl, 1,2,2,3-tetramethyl--1-cyclobutyl, 1,2,3,3-tetramethyl--1-cyclobutyl, 2,2,3,3-tetramethyl--1-cyclobutyl, 2,3,3,4-tetramethyl--1-cyclobutyl, 1,2,2,3-tetramethyl--1-cyclopentyl, 1,2,2,4-tetramethyl--1-cyclopentyl, 1,2,2,5-tetramethyl--1-cyclopentyl, 1,2,3,3-tetramethyl--1-cyclopentyl, 1,2,3,4-tetramethyl--1-cyclopentyl, 1,2,3,5-tetramethyl--1-cyclopentyl, 1,2,5,5-tetramethyl--1-cyclopentyl, 2,2,3,3-tetramethyl--1-cyclopentyl, 2,2,3,3-tetramethyl--1-cyclohexyl, 2,2,4,4-tetramethyl--1-cyclohexyl, 2,2,5,5-tetramethyl--1-cyclohexyl, 3,3,4,4-tetramethyl--1-cyclohexyl, 3,3,5,5-tetramethyl--1-cyclohexyl, 1-ethyl-1-cyclopropyl, 1-ethyl-1-cyclobutyl, 1-ethyl-1-cyclopentyl, 1-ethyl-1-cyclohexyl), 1-ethyl-1-suberyl, 2-ethyl-1-cyclopropyl, 2-ethyl-1-cyclobutyl, 2-ethyl-1-cyclopentyl, 2-ethyl-1-cyclohexyl, 2-ethyl-1-suberyl, 3-ethyl-1-cyclobutyl, 3-ethyl-1-cyclopentyl, 3-ethyl-1-cyclohexyl, 3-ethyl-1-suberyl, 4-ethyl-1-cyclohexyl or 4-ethyl-1-suberyl.
According to the present invention, R
1and R
2also C3-to C10-alkylidene group can jointly be represented, wherein R
1and R
2jointly formed containing azo-cycle with the nitrogen of urea derivatives.Particularly can design like this, R
1and R
2common expression ethylidene, propylidene, butylidene, pentylidene or hexylidene, wherein these alkylidene groups itself can optionally be undertaken monosubstituted or polysubstituted by alkyl.R
1and R
2jointly form ethylenimine, azetidine, aza-cyclopentane, piperidine or azepan with the nitrogen of urea derivatives, itself can optionally carry out monosubstituted or polysubstituted with C1-to the C5-alkyl with above-mentioned implication.
According to the present invention ,-NHC (O) NR
1r
2represent and use radicals R on nitrogen N3
1and R
2replace and be bonded to the 1-urea groups (Ureayl) of basic structure by nitrogen N1, wherein R
1and R
2there is above-mentioned implication.
According to the present invention, halogen represents fluorine, chlorine or bromine especially.
According to the present invention, aryl represents the aromatic, aryl with 3 to 20 carbon atoms especially, and itself can carry out monosubstituted or polysubstituted by preferred C1-to the C5-alkyl with having above-mentioned implication further.Particularly preferably can design like this, use phenyl, naphthyl, anthryl or perylene base as aryl, itself can carry out monosubstituted or polysubstituted with C1-to the C5-alkyl with above-mentioned implication.Therefore aryl represents toluyl, xylyl, pseudo-cumyl or trimethylphenyl especially.
According to the present invention, aralkyl represents the C1-C15-alkyl with above-mentioned implication replaced with the aryl with above-mentioned implication.Especially, aralkyl can represent phenmethyl.
Particularly preferably, liquid curing-agent according to the present invention comprises the aliphatic urea derivatives of at least one according to formula (I).In the described aliphatic urea derivatives according to formula (I), R
1and R
2represent hydrogen or C1-to C15-alkyl, R simultaneously or independently of one another
3implication be hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, use-NHC (O) NR
1r
2c1-to the C15-alkyl replaced or with-NHC (O) NR
1r
2c1-to the C15-cycloalkyl replaced.
Particularly preferably, liquid curing-agent according to the present invention comprises the urea derivatives of at least one formula (I), wherein at least one radicals R
1and R
2represent methyl.Particularly preferably be MU, 1,3-dimethyl urea or 1,1-dimethyl urea (i.e. R
1=R
2=methyl and R
3=H).
Further preferably according to the aliphatic urea derivatives of formula (I), wherein R
1and R
2there is above-mentioned implication, particularly hydrogen, methyl or ethyl, and R
3represent with-NHC (O) NR
1r
2c1-to the C15-cycloalkyl replaced.Very particularly preferably be the liquid curing-agent of the aliphatic urea derivatives comprised according to formula (II)
Wherein group is simultaneously or meet independently of one another:
R
1, R
2=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C10-alkylidene group by forming ring;
R
4, R
4 ', R
5, R
5 ', R
6, R
6 ', R
7, R
7 ', R
8, R
8 '=while or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl ,-NHC (O) NR
1r
2or with-NHC (O) NR
1r
2c1-to the C15-alkyl replaced.
The liquid curing-agent of the urea derivatives of further preferably contained (II), wherein R
1and R
2represent hydrogen or methyl simultaneously or independently of one another, and R
4, R
4 ', R
5, R
5 ', R
6, R
6 ', R
7, R
7 ', R
8, R
8 'simultaneously or represent hydrogen, methyl, ethyl ,-NHC (O) NR independently of one another
1r
2or with-NHC (O) NR
1r
2the methyl replaced or ethyl.Particularly preferably be 1-(N, N-dimethyl urea)-3-(N, N-dimethyl urea methyl)-3,5,5-trimethyl-cyclohexane, is hereafter also referred to as N'-[3-[[[(dimethylamino) carbonyl] is amino] methyl]-3,5,5-trimethylcyclohexyl]-N, N-dimethyl-urea (i.e. R
1=R
2=R
5=R
5 '=R
7=methyl, and R
7 '=-CH
2-NHC (O) N (CH
3)
2, and R
4=R
4 '=R
6=R
6 '=R
8=R
8 '=hydrogen).
But also can design like this in a substituting embodiment, liquid curing-agent according to the present invention comprises aromatics urea derivatives.Therefore described liquid curing-agent comprises the urea derivatives of at least one formula (I), wherein radicals R
3=aryl, aralkyl, use-NHC (O) NR
1r
2the aryl replaced or with-NHC (O) NR
1r
2the aralkyl replaced represents the group of general formula (III)
Wherein radicals R
1, R
2there is above-mentioned implication and other group simultaneously or meet independently of one another:
R
4, R
5, R
6, R
7, R
8=hydrogen, halogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, aryl, aralkyl ,-CF
3,-NHC (O) NR
1r
2, with-NHC (O) NR
1r
2c1-to the C15-alkyl, use-NHC (O) NR that replace
1r
2the aryl replaced, or with-NHC (O) NR
1r
2the aralkyl replaced;
R
9, R
10=while or independently of one another hydrogen or C1-to C5-alkyl;
Number between n=0 and 10.
In described aromatics urea derivatives, particularly preferably such urea derivatives, wherein radicals R
4, R
5, R
6, R
7and R
8simultaneously or represent hydrogen, C1-to C15-alkyl ,-NHC (O) NR independently of one another
1r
2, with-NHC (O) NR
1r
2c1-to the C15-aryl replaced or with-NHC (O) NR
1r
2c1-to the C15-arylalkyl replaced.The liquid curing-agent of the urea derivatives of further preferably contained (IV)
Wherein R
1, R
2, R
4and R
5there is above-mentioned implication and especially simultaneously or represent hydrogen, C1-C15-alkyl independently of one another.Preferably, about formula (VI), radicals R
1and R
2represent methyl.Particularly preferably be 1,1 '-(4-methyl-metaphenylene)-bis--(3,3-dimethyl urea) and 1,1 '-(2-methyl-metaphenylene)-bis--(3,3-dimethyl urea) (i.e. R
1=R
2=R
5methyl, and R
4for hydrogen).
Can design especially like this according to another embodiment, liquid curing-agent according to the present invention comprises, particularly contain a) cyanamide, b) urea derivatives of two kinds of formulas (I) different from each other, (II) and/or (IV), and c) at least one viscosity modifier, wherein said liquid curing-agent is also preferred with the cyanamide of 1:1 to 4:1: the molar ratio of urea derivatives or urea derivatives mixture comprises the urea derivatives of cyanamide and two kinds of formulas (I) different from each other, (II) and/or (IV).
According to another embodiment of the invention, theme of the present invention is such liquid curing-agent, described solidifying agent comprises, particularly contain a) cyanamide, b) at least one urea derivatives, described urea derivatives is selected from urea, 1-MU, 1, 1-dimethyl urea, 1, 3-dimethyl urea, 3-(the chloro-4-aminomethyl phenyl of 3-)-1, 1-dimethyl urea, 3-(rubigan)-1, 1-dimethyl urea, 3-phenyl-1, 1-dimethyl urea, 3-(3, 4-dichlorophenyl)-1, 1-dimethyl urea, 1, 1 '-(methylene radical two-to phenylene)-bis--(3, 3-dimethyl urea), 3-(3-trifluoromethyl)-1, 1-dimethyl urea, 1, 1 '-(2-methyl-metaphenylene)-bis--(3, 3-dimethyl urea) and/or 1, 1 '-(4-methyl-metaphenylene)-bis--(3, 3-dimethyl urea), and c) at least one viscosity modifier, wherein also preferably use cyanamide and urea derivatives or urea derivatives mixture with the molar ratio of 1:1 to 4:1.
According to the present invention importantly, liquid curing-agent according to the present invention comprises at least one viscosity modifier, and described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, ether alcohol, polyether glycol, ketone, aldehyde, nitrile, carboxylicesters or its mixture.Viscosity modifier can raise according to the choice and application field of resin-composition to be prepared or reduce the viscosity of resin-composition to be prepared.Particularly preferably be the liquid curing-agent itself with the viscosity modifier of the boiling point of at least 100 DEG C comprising and be selected from described group.Properties-correcting agent to be retained in profiled member to be prepared when solidifying and preferred combination in the polymer matrix or polymeric matrix is cross-linked extraly.
Be selected from the viscosity modifier of monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, ether alcohol, polyether glycol or its mixture, those particularly itself with the boiling point of at least 100 DEG C are proved to be effective especially viscosity modifier.
In an especially preferred embodiment, liquid curing-agent comprises the viscosity modifier of at least one according to logical formula V, and described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, ether alcohol or polyether glycol or its mixture.
Wherein group is simultaneously or meet independently of one another:
R
11, R
22=while or independently of one another hydrogen ,-OH or C1-to C15-alkyl;
R
12, R
14, R
16, R
18, R
20=while or independently of one another hydrogen ,-OH or C1-to C5-alkyl;
R
13, R
15, R
17, R
19, R
21=while or independently of one another hydrogen ,-OH ,-NH
2or C1-to C5-alkyl;
Wherein
M, n, o, s, p, q, t=simultaneously or independently of one another 0 to 10, the particularly number of 0 to 5; And wherein
I) m, s, u=simultaneously or independently of one another 1 to 10, the particularly number of 1 to 5; And/or
Ii) p, t, u=simultaneously or independently of one another 1 to 10, the particularly number of 1 to 5.
Also preferably, can use and be selected from C2-to C10-amino alcohol and C6-to C12-alcohol, particularly 1-hexanol, 1-heptanol, 1-octanol, 1 nonyl alcohol, 1-decanol, 2-hexanol, 2-enanthol, sec-n-octyl alcohol, 2-nonyl alcohol, 2-decyl alcohol, 2-monoethanolamine, the monohydroxy-alcohol of 3-aminopropanol, 4-amino butanol, 5-aminopentanol, 6-amino-hexanol, the amino enanthol of 7-, the amino octanol of 8-, the amino nonyl alcohol of 9-, the amino decyl alcohol of 10-or its mixture, be selected from the dibasic alcohol of C2-to C12-alcohol, particularly ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol or its mixture; Be selected from the trivalent alcohol of C3-to C12-alcohol, particularly Glycerin, 1,2,3-trihydroxybutane, 1,2,3-penta triol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,6-hexanetriol or its mixture; Be selected from the aldehyde of C6-to C12-aldehyde, particularly hexanal, enanthaldehyde, octanal, aldehyde C-9, capraldehyde or its mixture; Ketone, particularly 2 pentanone, propione, methyl-n-butyl ketone, 3-hexanone, 2-heptanone, 3-heptanone, methyln-hexyl ketone, 3-octanone or its mixture; Be selected from dibutyl ether, diamyl ether, hexyl ether, diheptyl ether, dicaprylyl ether, dinonyl ether, didecyl ether, methoxyl group-and ethoxy alcohol, methoxyl group-and oxyethyl group glycol, polyoxyethylene glycol, polypropylene glycol, polyethylenepropylene glycol, polyalkylene glycol monoalkyl ether, particularly MPEG-550, polyethyleneglycol ethyl ether, ethylhexyl ether, ethylheptyl ether, ethyloctanyl ether, ethylnonanyl ether, ethyl decyl ethers, cyanophenyl, the ether of acetonitrile or its mixture, nitrile, polyethers, ether alcohol or polyether glycol.
In addition find under study for action, be selected from tetrahydroglyoxaline (be hereafter also referred to as 4 when adding at least one in liquid curing-agent further, 5-dihydro-1H-imidazoles) or the curing catalyst of imidazoles time, better processing can be provided comprising in the method for filling of the fluoropolymer resin-composition of the liquid curing-agent according to type described herein, particularly epoxy resin-composition or injecting method and preimpregnation method.
Can mix in liquid curing-agent according to the present invention and be selected from the tetrahydroglyoxaline according to formula (VI) or the curing catalyst according to the imidazoles of formula (VII) and do not affect its liquid state, and be applicable to fluoropolymer resin with flying colors, the solidification of particularly curable polymeric resin, particularly curable epoxy, curable polyurethane resin or its mixture.Its mode of action is in the epoxy suitable with the curing performance of the Dyhard RU 100 accelerated with imidazoles and be <100 DEG C.However, the latent of a couple of days to several weeks is at room temperature still obtained.
Therefore according to another embodiment, theme of the present invention is also liquid curing-agent, described solidifying agent comprises d) at least one and is selected from curing catalyst according to the tetrahydroglyoxaline of formula (VI) or the imidazoles according to formula (VII), and wherein tetrahydroglyoxaline and imidazoles have following structure
And wherein group is simultaneously or meet independently of one another:
R
30=while or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, aryl, aralkyl;
R
32, R
34=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C15-alkylidene group by forming ring;
R
33, R
35=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C15-alkylidene group by forming ring.
The basic liquid mixture that described tetrahydroglyoxaline and imidazoles and cyanamide and at least one describe the urea derivatives of type herein combines has the fabulous effect as curing catalyst, and wherein liquid properties can not noticeable change and existing with the form of liquid curing-agent.In addition have been surprisingly found that especially, compared to stock blend or the liquid curing-agent without curing catalyst, the latent of described liquid curing-agent is improved, and therefore storage power can raise.Therefore can provide solidifying agent in a word, described solidifying agent due to the high latent in fluoropolymer resin-composition and in fluoropolymer resin-composition hyperergy at curing temperatures and being suitable for use in flying colors in method for filling or injecting method.
Particularly preferably, in one embodiment of the invention, liquid curing-agent can comprise the curing catalyst be selected from according to the tetrahydroglyoxaline of formula (VI) or the imidazoles according to formula (VII), and wherein group is simultaneously or meet independently of one another:
R
30=hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl or phenyl;
R
32, R
34=while or independently of one another hydrogen, C1-to C5-alkyl or phenyl;
R
33, R
35=while or independently of one another hydrogen, C1-to C5-alkyl or phenyl.
Very particularly preferably, the tetrahydroglyoxaline according to formula (VI) or the imidazoles according to formula (VII) can be used as curing catalyst according to the present invention, it is selected from 2-methyl isophthalic acid H-imidazoles, 2-ethyl-1H-imidazoles, 2-propyl group-1H-imidazoles, 2-butyl-1H-imidazoles, 2-amyl group-1H-imidazoles, 2-hexyl-1H-imidazoles, 2-heptyl-1H-imidazoles, 2-octyl group-1H-imidazoles, 2-nonyl-1H-imidazoles, 2-decyl-1H-imidazoles, 2-phenyl-1H-imidazoles, 2-methyl isophthalic acid H-tetrahydroglyoxaline, 2-ethyl-1H-tetrahydroglyoxaline, 2-propyl group-1H-tetrahydroglyoxaline, 2-butyl-1H-tetrahydroglyoxaline, 2-amyl group-1H-tetrahydroglyoxaline, 2-hexyl-1H-tetrahydroglyoxaline, 2-heptyl-1H-tetrahydroglyoxaline, 2-octyl group-1H-tetrahydroglyoxaline, 2-nonyl-1H-tetrahydroglyoxaline, 2-decyl-1H-tetrahydroglyoxaline and/or 2-phenyl-1H-tetrahydroglyoxaline.Compared to 1-alkyl imidazole, described imidazoles unexpectedly improves latent further and therefore raises the stability in storage of liquid curing-agent.
The embodiment favourable according to another, therefore theme of the present invention is also the liquid curing-agent of the solidification for curable polymeric resin, described solidifying agent comprises, particularly contain a) cyanamide, b) at least one formula (I), and/or the urea derivatives of (IV) (II), c) viscosity modifier, particularly according to the viscosity modifier of formula (V), with d) at least one is selected from the curing catalyst according to the tetrahydroglyoxaline of formula (VI) or the imidazoles according to formula (VII), wherein liquid curing-agent is preferably with the cyanamide of 1:1 to 4:1: the molar ratio of urea derivatives or urea derivatives mixture comprises cyanamide and at least one formula (I), or the urea derivatives of (IV) (II).
Be selected from according under the tetrahydroglyoxaline of formula (VI) or the existence according to the curing catalyst of the imidazoles of formula (VII) at least one, cyanamide: the molar ratio of urea derivatives also can drop on outside the preferable range of 1:1 to 4:1.Such as, 0.1 to <1:1, the particularly cyanamide of 0.2 to <1:1: the molar ratio of urea derivatives is possible, the cyanamide of >4:1 to 20:1, particularly >4:1 to 10:1: the molar ratio of urea derivatives is also possible.
Also have been surprisingly found that, when add further in solidifying agent be selected from inorganic or organic acid stablizer time, solidifying agent itself can be regulated and comprise the extra high latent of epoxy resin-composition of described solidifying agent and therefore high stability in storage.Be selected from inorganic or organic acid stablizer by adding, latent can double, and is even increased to three times in some cases.Compared to the solidifying agent without stablizer, maintain outstanding curing performance, such as, hyperergy under solidification value simultaneously.
Therefore according to another embodiment, the present invention also comprises liquid curing-agent, and described solidifying agent preferably comprises further and e) is selected from inorganic or organic acid stablizer.
Discovery is particularly selected from aromatics and non-aromatic carboxylic acid, dicarboxylic acid or tricarboxylic organic acid are particularly suitable as stablizer.Also preferably, can use especially and be selected from following acid as organic acid or as aromatics and non-aromatic carboxylic acid, dicarboxylic acid or tricarboxylic acid: formic acid, acetic acid, propionic acid, toxilic acid, propanedioic acid, Whitfield's ointment, lactic acid, citric acid, oxalic acid, hexanodioic acid, phenylformic acid, phthalic acid, alkyl-sulfonic acid, aryl sulfonic acid, particularly toluenesulphonic acids, or its acid anhydrides.
Also can design like this, solidifying agent according to the present invention comprises and is selected from following organic acid as stablizer: hydrochloric acid, sulfuric acid, sulfur acid, phosphoric acid, phosphoric acid, ortho-phosphoric acid, bisphosphate, triphosphoric acid, Tripyrophosphoric acid, nitric acid or its acid anhydrides.
Therefore theme of the present invention is also liquid curing-agent, described solidifying agent comprise be selected from Whitfield's ointment, phthalic acid, toluenesulphonic acids, sulfuric acid, phosphoric acid or its acid anhydrides or its mixture inorganic or organic acid as stablizer.
The embodiment favourable according to another, therefore theme of the present invention is also the liquid curing-agent of the solidification for curable polymeric resin, and described solidifying agent comprises, particularly contain a) cyanamide, b) at least one formula (I), and/or the urea derivatives of (IV) (II), c) at least one viscosity modifier, particularly according to the viscosity modifier of formula (V), with d) optional at least one is selected from the curing catalyst according to the tetrahydroglyoxaline of formula (VI) or the imidazoles according to formula (VII), and e) at least one stablizer, described stablizer is selected from organic acid, particularly aromatics and non-aromatic carboxylic acid, dicarboxylic acid or tricarboxylic acid, or mineral acid, be particularly selected from hydrochloric acid, sulfuric acid, sulfur acid, phosphoric acid, phosphoric acid, ortho-phosphoric acid, bisphosphate, triphosphoric acid, Tripyrophosphoric acid, the mineral acid of nitric acid or its acid anhydrides, wherein liquid curing-agent is particularly with the cyanamide of 1:1 to 4:1: the molar ratio of urea derivatives or urea derivatives mixture comprises the urea derivatives of cyanamide and at least one formula (I).
Under the existence of at least one stablizer, cyanamide: the molar ratio of urea derivatives also can drop on outside the preferable range of 1:1 to 4:1.Such as, 0.1 to <1:1, the particularly cyanamide of 0.2 to <1:1: the molar ratio of urea derivatives is possible, the cyanamide of >4:1 to 20:1, particularly >4:1 to 10:1: the molar ratio of urea derivatives is also possible.
Particularly preferably be acid, particularly mineral acid that water-content is less than 20 % by weight (in acid).Very particularly preferably be that water-content is less than 15 % by weight, be more preferably less than 10 % by weight and be less than the acid, particularly mineral acid of 5 % by weight (respectively in acid) very especially.Therefore this as liquid and in the sense of the present invention not solvent-laden liquid curing-agent can be provided.
According to a particularly preferred embodiment of the present invention, liquid curing-agent comprises
A) cyanamide of 1 to 50 weight part,
B) at least one formula (I) of 1 to 50 weight part, the urea derivatives of (II) and/or (IV),
C) at least one viscosity modifier of 0.01 to 50 weight part,
D) curing catalyst of the tetrahydroglyoxaline of the formula that is selected from (VI) of 0 to 10 weight part and/or the imidazoles of formula (VII), and
E) at least one stablizer of 0 to 10 weight part.
In embodiments of the invention, theme of the present invention is epoxy resin-composition and urethane resin-composition equally, described epoxy resin-composition comprises a) at least one curable epoxy, and b) at least one according to the liquid curing-agent of the above-mentioned type, described urethane resin-composition comprises a) at least one curable polyurethane resin, and b) at least one according to the liquid curing-agent of the above-mentioned type.
About curable epoxy resin, the present invention does not limit.Can consider there is more than one 1,2-epoxide group (oxyethane) usually and can be saturated or unsaturated, aliphatic, cyclic aliphatic, aromatics or heterocycle all commercially available prod.Epoxy resin can also have substituting group, such as halogen, phosphorus group and hydroxyl.Based on 2, the glycidyl polyethers (dihydroxyphenyl propane) of two (4-hydroxy phenyl) propane of 2-and the derivative (tetrabromo-bisphenol), 2 with bromine replacement thereof, the two glycidyl polyethers (Bisphenol F) of (4-hydroxy phenyl)-methane of 2-and the glycidyl polyethers of phenolic varnish and can be cured particularly well by use solidifying agent according to the present invention based on the epoxy resin of the aniline (such as p-aminophenol or 4,4'-diaminodiphenyl-methane) of aniline or replacement.
Consumption according to liquid curing-agent of the present invention does not limit.But preferably, with 100 parts of resins, particularly curable epoxy or curable polyurethane resin meter, use 0.01 to 15 part, preferably 0.1 to 15 part, preferably 0.1 to 10 part and very particularly preferably 1 to 10 part (respectively by weight).The present invention also covers the multiple combination according to liquid curing-agent of the present invention or the combination according to liquid curing-agent of the present invention and other co-curing agent.
Solidification by means of the epoxy resin according to solidifying agent used in the present invention is carried out usually at higher than the temperature of 80 DEG C.The selection of solidification value is depended on specific processing request and product requirement and can when preparing mainly due to the adjustment of curing dose and change due to adding of other additive.In resin formulations, introduce energy is in which way unessential.Such as, energy can be introduced with form of heat by stove or heating unit, also can stimulate by means of ir emitter or by microwave or other ray and realize introducing energy.
By adding other commercially available additives, as those skilled in the art are used for known those of cured epoxy resin, the solidification situation according to preparaton of the present invention can change.
For improvement of the workability of uncured epoxy resin-composition or uncured urethane-composition additive or comprise such as reactive diluent, filler, rheologic additive such as thixotropic agent or dispersing additive, defoamer, dyestuff, pigment, plasticized modifier, impact modifier or fire-proof additive for the additive of the thermomechanical property adaption demand making thermoset articles prepared therefrom.
Comprise and be not only applicable to manual working method but also applicable machining method according to the epoxy resin-composition of solidifying agent of the present invention, and be particularly suitable for fortifying fibre and the matrix material of preparing dipping, the such as special paper Faserverbund-Kunststoffe (2006 at G.W.Ehrenstein, 2nd edition, Carl Hanser press, Munich, 5th chapter, 148ff page) and the paper Composite Solutions (2006 of M.Reyne, JEC Publications, 5th chapter, 51ff page) middle description.Except being used in except in preimpregnation method, in method for filling and injecting method, process is particularly preferred form processing.Favourable according to liquid curing-agent of the present invention usually fabulous miscibility in the epoxy, because for dipping method, it is necessary (especially see M.Reyne for having low viscous flowable perfusion resin, Composite Solutions, 2006, JEC Publications, the 5th chapter, the 65th page; And G.W.Ehrenstein, Faserverbund-Kunststoffe, the 2006,2nd edition, Carl Hanser press, Munich, the 5th chapter, the 166th page).
Therefore, theme of the present invention is also matrix material, and described matrix material comprises a) solid support material, particularly filamentary material, b) at least one curable epoxy and/or curable polyurethane resin, and the liquid curing-agent of c) at least one the above-mentioned type.
Therefore theme of the present invention is the purposes of liquid curing-agent for the solidification of curable compositions of the above-mentioned type equally.Especially, described purposes relates to the composition comprising at least one curable epoxy and/or curable polyurethane resin.
In addition, the present invention also comprises the purposes of liquid curing-agent for the solidification through the filamentary material of dipping or fabric, knitted fabrics or the cloth through flooding of the above-mentioned type.
Due to favourable application performance and the low amount of being metered into thereof of liquid curing-agent according to the present invention, realize favourable cost proportion of utilization, therefore described solidifying agent is specially adapted to industrial application.
Embodiment
1) raw material used:
Cyanamide: AlzChem AG
Urea B1:1,1-bis-MU – (AlzChem AG)
Urea B2:1,1 '-(4-methyl-metaphenylene)-bis--(3,3-dimethyl urea) – (AlzChem AG)
Urea B4:N'-[3-[[[(dimethylamino) carbonyl] is amino] methyl]-3,5,5-trimethylcyclohexyl]-N, N-dimethyl-Niao – (AlzChem AG)
E 828LVEL: epoxy resin Epikote 828LVEL – (Momentive company)
RIMR 135: Huan oxygen tree Zhi – (Momentive Specialty Chemicals company)
RIMH 137: liquid amine hardener – (Momentive Specialty Chemicals company)
Vestamin IPDA: liquid amine hardener – (Evonik Degussa GmbH company)
Properties-correcting agent M1:1-hexanol (boiling point 157 DEG C of) – (Merck company)
Properties-correcting agent M2: ethylene glycol (boiling point 197 DEG C of) – (Merck company)
Properties-correcting agent M3: hexanetriol (boiling point 178 DEG C of) – (Evonik Degussa GmbH company)
Properties-correcting agent M4:3-pentanone (boiling point 102 DEG C of) – (Baker company)
Properties-correcting agent M5: octanal (boiling point 171 DEG C of) – (Merck company)
Properties-correcting agent M6: cyanophenyl (boiling point 191 DEG C of) – (AlzChem AG, Trostberg)
Properties-correcting agent M7: etheric acid ethyl ester (boiling point 180 DEG C of) – (Fluka company)
Properties-correcting agent M8: methyl alcohol (boiling point 124 DEG C of) – (Roth company)
Properties-correcting agent M9:2-monoethanolamine (boiling point 172 DEG C of) – (Roth company)
Properties-correcting agent M10: diacetyl oxide (boiling point 139 DEG C of) – (Merck company)
Promotor I1:2-methyl isophthalic acid H-Mi Zuo – (AlzChem AG)
Promotor I2:1-Jia base Mi Zuo – (Roth company)
Promotor I3:2-phenyl-1H-Mi Zuo – (AlzChem AG)
Promotor I4:2-phenyl-1H-Mi Zuo Lin – (AlzChem AG)
Promotor I5:4,5-dihydro-2-nonyl-1H-Mi Zuo – (AlzChem AG)
Promotor I6:2-nonyl-1H-Mi Zuo – (AlzChem AG)
table 3:there is viscosity modifier to Cheng – molar ratio/[mol:mol] with the Zu of the liquid curing-agent of curing catalyst according to of the present invention
| According to the starting mixt of table 1 | Starting mixt | M3 | Liquid curing-agent |
| H6I1 | 1 | 0.276 | H6I1M3 |
| H6I2 | 1 | 0.276 | H6I2M3 |
| H6I3 | 1 | 0.276 | H6I3M3 |
| H6I4 | 1 | 0.276 | H6I4M3 |
| H6I5 | 1 | 0.276 | H6I5M3 |
| H6I6 | 1 | 0.276 | H6I6M3 |
| H7I1 | 1 | 0.276 | H7I1M3 |
2) preparation of liquid curing-agent
a) there is viscosity modifier and curing catalyst
Device: 500ml double-walled reaction vessel, thermostatted, KPG-agitator, 3 blade metal agitators, thermometer, powder funnel,
Program: first add cyanamide, different urea (B1, B2, B4), viscosity modifier (M3) and curing catalyst (I1-I6) by powder funnel in reaction vessel.Then to double-walled reaction vessel supply 40 to 42 DEG C warm water and open 3 blade metal agitators (200 turns/Min) according to viscosity modifier, under the internal temperature of 35 to 40 DEG C, in 20 to 40 minutes, prepare liquid curing-agent.Then liquid curing-agent is cooled to 20 to 25 DEG C, is transferred in Glass Containers and stores at 23 DEG C.
b) there is viscosity modifier
Device: 500ml double-walled reaction vessel, thermostatted, KPG-agitator, 3 blade metal agitators, thermometer, powder funnel,
Program: first add cyanamide, different urea (B1, B2, B4) and viscosity modifier (M1-M10) by powder funnel in reaction vessel.Then to double-walled reaction vessel supply 40 to 42 DEG C warm water and open 3 blade metal agitators (200 turns/Min).According to viscosity modifier, under the internal temperature of 35 to 40 DEG C, in 20 to 40 minutes, prepare liquid curing-agent.Then liquid curing-agent is cooled to 20 to 25 DEG C, is transferred in Glass Containers and stores at 23 DEG C.
3) use-test-result: according to the performance of epoxy resin-composition of the present invention
A) according to the composition of epoxy resin-composition of the present invention
For use test, use with identical blending ratio (being respectively the epoxy resin of 100 weight parts, the liquid curing-agent of 10 weight parts) epoxy resin-composition had according to liquid curing-agent of the present invention.
B) according to the preparation of epoxy resin-composition of the present invention
Weigh in 250ml dispersion cup put into the epoxy resin (Epikote 828 LVEL) of 100 weight parts and 10 weight parts mix 2 minute at dissolver with 500 turns/min according to solidifying agent of the present invention according to what show 1-3.Then mixture is made degassed 10 minutes in a vacuum.
C) for determining the measuring method of performance
ο Dyn-DSC: measurement standard 30-250 DEG C, rate of heating 10K/min on Mettler Toledo DSC 822
ο glass point: measure Tg 3 heating on Mettler Toledo DSC 822
200 DEG C are heated to from 30 DEG C with 20K/min
10.0min is kept at 200 DEG C
50 DEG C are cooled to from 200 DEG C with 20K/min
5.0min is kept at 50 DEG C
200 DEG C are heated to from 50 DEG C with 20K/min
10.0min is kept at 200 DEG C
50 DEG C are cooled to from 200 DEG C with 20K/min
5.0min is kept at 50 DEG C
220 DEG C are heated to from 50 DEG C with 20K/min
ο viscosity: measure on HAAKE Rheostress 1 and carry out at 25 DEG C, represent with Pa*s, uses rotating cone 1 DEG C of 35/1Ti
velocity of shear 5.01/s (reciprocal seconds)
ο gel time: on metal block-thermostatted VLM 2.0/-HAT ALU-Steck-Kappen (
measure at 140 DEG C highly)
ο latent: the storage power that epoxy resin-composition represents with sky (d) after storing in climate box at 23 DEG C.
The definition of latent: with the time that sky (d) represents after the viscosity of epoxy resin-composition doubles.The terminal of storage power is arrived at this time point.
table 4:epoxy resin-composition liquid curing-agent and performance thereof
*: not according to the invention
*: not according to the invention, uses epoxy resin E828 – (Momentiv Speciality Chemicals company), 100 parts of epoxy resin: 23 parts of Vestamin IPDA – (Evonik Degussa GmbH company)
* *: not according to the invention, uses epoxy resin RIMR 135 – (Momentiv Speciality Chemicals company), 100 parts of epoxy resin: 30 parts of RIMH 137 – (Momentiv Speciality Chemicals company)
The liquid curing-agent of the different viscosity modification listed in table 4 and the reaction result of epoxy resin are clear to be shown, and the second-order transition temperature (Tg) of viscosity modifier on resulting polymers does not almost affect.But it is significant on the impact of viscosity (as intended), latent and gel time.Inhomogeneous viscosity modifier can produce Different Effects to the liquid curing-agent of viscosity modifier according to the present invention.
When solidifying agent H5 and H6, although monohydroxy-alcohol, dibasic alcohol, ketone, nitrile and ether produce fall low viscous effect, trivalent alcohol raises viscosity.Aldehyde plays viscosity neutrality.When solidifying agent H6, the also low viscous effect of landing of ester and acid anhydrides, and amino alcohol raises viscosity.Solidifying agent H5 and the viscosity modifier spontaneous reaction being selected from ester, acid anhydrides and amino alcohol, therefore can not measure viscosity, gel time and latent.
But different viscosity modifiers produces impact violent especially to the stability in storage (latent) of different epoxy resin/curing agent mixtures and reactivity thereof.When solidifying agent H5, monohydroxy-alcohol, dibasic alcohol, aldehyde and nitrile make latent reduce half, and trivalent alcohol, ketone and ether make latent be increased to more than three times.The latent of epoxy resin/H6 mixture is inconsistent, and dibasic alcohol and nitrile also make stability in storage be increased to three times.
Gel time provides the information of the response capacity about epoxy resin/curing agent mixture.Interestingly, viscosity modifier can shorten gel time and other can extend gel time.Monohydroxy-alcohol and the usual accelerated reaction of dibasic alcohol, and trivalent alcohol, ketone and ether delayed response.The reaction of aldehyde and nitrile fast curing additives H5, but delay the reaction of solidifying agent H6.When H6, ester and acid anhydrides also play retarding action, the certain accelerated reaction of amino alcohol and can not spontaneous reaction.
When the liquid curing-agent of viscosity modifier is used imidazole modified in its composition, although observe the further shortening of gel time and therefore observe reactive rising, all the time along with the remarkable rising of viscosity and stability in storage (latent).
Compared to this, known and conventional liquid amine solidifying agent such as RIMH 137 (Momentiv Speciality Chemicals company) or IPDA (Evonik Degussa GmbH company) are although demonstrate low solidification value, mixture according to the present invention starts polymerization in the suitable time and realizes much higher second-order transition temperature, but has much bigger latent.
By using viscosity modifier and imidazoles in the liquid curing-agent of viscosity modifier according to the present invention, produce described liquid curing-agent as a series of special behavior pattern required in many application in mixture field.Due to the performance of described wide region, the liquid curing-agent according to viscosity modifier of the present invention almost can adapt to all needs individually.
table 5:test with the perfusion of the epoxy resin-composition according to table 4
table 6:for pouring into the fiber Fu He Wu – structure of test
Mould: hot plate
Supply container: beaker
Vacuum: vacuum pump standard (15-20mbar)
testing sequence:
Mixing and preheating ring epoxy resins-composition E2, E20 in heatable supply container.Import flexible pipe enter and be fixed to supply container, discharge hose (see the structure of perfusion test, table 5) is connected with vacuum pump by safety valve, opens described pump.Hot plate (its simulation can heating mould) is made to reach filling temperature.Epoxy resin-composition is made to be aspirated through fibre composites by arranging vacuum.After thorough impregnation, take and seal importing flexible pipe and discharge hose apart, hot plate makes total solidify to form laminate.After solidifying completely and cooling, from structure, removing layer is fit.
Claims (15)
1., for fluoropolymer resin, the liquid curing-agent of the solidification of particularly curable polymeric resin, particularly epoxy resin, described solidifying agent comprises
A) cyanamide;
B) urea derivatives of at least one formula (I)
Wherein group meets as follows and at least one radicals R simultaneously or independently of one another
1, R
2, R
3be not hydrogen:
R
1, R
2=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C10-alkylidene group by forming ring;
R
3=hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, aryl, aralkyl, use-NHC (O) NR
1r
2c1-to the C15-alkyl, use-NHC (O) NR that replace
1r
2c3-to the C15-cycloalkyl, use-NHC (O) NR that replace
1r
2the aryl replaced, or with-NHC (O) NR
1r
2the aralkyl replaced;
With
C) at least one viscosity modifier, described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, polyethers, polyether glycol, ketone, aldehyde, nitrile, carboxylicesters or its mixture.
2. liquid curing-agent according to claim 1, is characterized in that, described solidifying agent is with the cyanamide of 1:1 to 4:1: the molar ratio of urea derivatives or urea derivatives mixture comprises the urea derivatives of cyanamide and at least one formula (I).
3. liquid curing-agent according to claim 1 and 2, is characterized in that, radicals R
3=aryl, aralkyl, use-NHC (O) NR
1r
2the aryl replaced or with-NHC (O) NR
1r
2the aralkyl replaced represents the group of general formula (III)
Wherein radicals R
1, R
2there is above-mentioned implication and other group simultaneously or meet independently of one another:
R
4, R
5, R
6, R
7, R
8=hydrogen, halogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, aryl, aralkyl ,-CF
3,-NHC (O) NR
1r
2, with-NHC (O) NR
1r
2c1-to the C15-alkyl, use-NHC (O) NR that replace
1r
2the aryl replaced, or with-NHC (O) NR
1r
2the aralkyl replaced;
R
9, R
10=while or independently of one another hydrogen or C1-to C5-alkyl;
Number between n=0 and 10.
4. the liquid curing-agent according at least one item of aforementioned claim, is characterized in that, the urea derivatives of described solidifying agent contained (I), and wherein group is simultaneously or meet independently of one another:
R
1, R
2=while or independently of one another hydrogen or C1-to C15-alkyl;
R
3=hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl, use-NHC (O) NR
1r
2c1-to the C15-alkyl replaced, or with-NHC (O) NR
1r
2c3-to the C15-cycloalkyl replaced.
5. the liquid curing-agent according at least one item of aforementioned claim, it is characterized in that, described solidifying agent comprises the urea derivatives according to formula (I), described urea derivatives is selected from 1-MU, 1, 1-dimethyl urea, 1, 3-dimethyl urea, 3-(the chloro-4-aminomethyl phenyl of 3-)-1, 1-dimethyl urea, 3-(rubigan)-1, 1-dimethyl urea, 3-phenyl-1, 1-dimethyl urea, 3-(3, 4-dichlorophenyl)-1, 1-dimethyl urea, 1, 1 '-(methylene radical two-to phenylene)-bis--(3, 3-dimethyl urea), 3-(3-trifluoromethyl)-1, 1-dimethyl urea, 1, 1 '-(2-methyl-metaphenylene)-bis--(3, 3-dimethyl urea) and/or 1, 1 '-(4-methyl-metaphenylene)-bis--(3, 3-dimethyl urea).
6. the liquid curing-agent according at least one item of aforementioned claim, it is characterized in that, described solidifying agent comprises viscosity modifier, described viscosity modifier itself has the boiling point of at least 100 DEG C.
7. the liquid curing-agent according at least one item of aforementioned claim, it is characterized in that, described solidifying agent comprises the viscosity modifier of at least one according to logical formula V, described viscosity modifier is selected from monohydroxy-alcohol, dibasic alcohol and/or polyvalent alcohol, ether, ether alcohol, polyethers or polyether glycol or its mixture
Wherein group is simultaneously or meet independently of one another:
R
11, R
22=while or independently of one another hydrogen ,-OH or C1-to C10-alkyl;
R
12, R
14, R
16, R
18, R
20=while or independently of one another hydrogen ,-OH or C1-to C5-alkyl;
R
13, R
15, R
17, R
19, R
21=while or independently of one another hydrogen ,-OH ,-NH
2or C1-to C5-alkyl;
Wherein
M, n, o, s, p, q, t=simultaneously or independently of one another 0 to 10 number, and wherein
I) m, s, u=simultaneously or independently of one another 1 to 10 number, and/or
Ii) p, t, u=simultaneously or independently of one another 1 to 10 number.
8. the liquid curing-agent according at least one item of aforementioned claim, is characterized in that, described solidifying agent also comprises d) at least one and is selected from curing catalyst according to the tetrahydroglyoxaline of formula (VI) or the imidazoles according to formula (VII)
Wherein group is simultaneously or meet independently of one another:
R
30=while or independently of one another hydrogen, C1-to C20-alkyl, C3-to C20-cycloalkyl, aryl, aralkyl;
R
32, R
34=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C15-alkylidene group by forming ring;
R
33, R
35=simultaneously or independently of one another hydrogen, C1-to C15-alkyl, C3-to C15-cycloalkyl or jointly represent C3-to C15-alkylidene group by forming ring.
9. the liquid curing-agent according at least one item of aforementioned claim, it is characterized in that, described solidifying agent also comprises e) stablizer, described stablizer is selected from inorganic or organic acid.
10. the liquid curing-agent according at least one item of aforementioned claim, is characterized in that, comprise be selected from Whitfield's ointment, phthalic acid, toluenesulphonic acids, sulfuric acid, phosphoric acid or its acid anhydrides or their mixture inorganic or organic acid as stablizer.
11. liquid curing-agents according at least one item of aforementioned claim, it is characterized in that, described solidifying agent comprises
The cyanamide of 1 to 50 weight part,
The urea derivatives of at least one formula (I) of 1 to 50 weight part,
At least one viscosity modifier of 0.01 to 50 weight part
The curing catalyst of the tetrahydroglyoxaline of the formula that is selected from (VI) of 0 to 10 weight part and/or the imidazoles of formula (VII), and
At least one stablizer of 0 to 10 weight part.
12. epoxy resin-composition, comprises
A) at least one curable epoxy, and
B) liquid curing-agent of at least one according at least one item of aforementioned claim 1 to 11.
13. urethane resins-composition, comprises
A) at least one curable polyurethane resin, and
B) liquid curing-agent of at least one according at least one item of aforementioned claim 1 to 11.
14. matrix materials, comprise
A) solid support material, particularly filamentary material,
B) at least one curable epoxy and/or curable polyurethane resin, and
C) liquid curing-agent of at least one according at least one item of aforementioned claim 1 to 11.
15. liquid curing-agents according at least one item of aforementioned claim 1 to 11 are used for the purposes of the solidification of the filamentary material through dipping or the fabric through dipping, knitted fabrics or cloth.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201210015315 DE102012015315A1 (en) | 2012-08-02 | 2012-08-02 | Liquid curing agent useful for curing polymer resins, preferably curable polymer resins comprising epoxide resins, preferably impregnated fiber materials or impregnated fabrics, comprises cyanamide, urea derivative, and viscosity modifier |
| DE102012015315.5 | 2012-08-02 | ||
| DE102012015316.3 | 2012-08-02 | ||
| DE201210015316 DE102012015316A1 (en) | 2012-08-02 | 2012-08-02 | Liquid curing agent useful for curing polymer resins, preferably curable polymer resins comprising epoxide resins, preferably impregnated fiber materials or impregnated fabrics, comprises cyanamide, urea derivative, and viscosity modifier |
| PCT/EP2013/066078 WO2014020060A2 (en) | 2012-08-02 | 2013-07-31 | Liquid hardeners for hardening epoxide resins (i) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104334602A true CN104334602A (en) | 2015-02-04 |
| CN104334602B CN104334602B (en) | 2017-09-19 |
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ID=48906261
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380029718.7A Active CN104334602B (en) | 2012-08-02 | 2013-07-31 | Liquid curing-agent for the solidification of epoxy resin (I) |
| CN201380040235.7A Active CN104507997B (en) | 2012-08-02 | 2013-07-31 | Liquid curing-agent for the solidification of epoxy resin (II) |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380040235.7A Active CN104507997B (en) | 2012-08-02 | 2013-07-31 | Liquid curing-agent for the solidification of epoxy resin (II) |
Country Status (15)
| Country | Link |
|---|---|
| US (2) | US9499659B2 (en) |
| EP (3) | EP2880072B1 (en) |
| JP (3) | JP6388288B2 (en) |
| KR (2) | KR20150041005A (en) |
| CN (2) | CN104334602B (en) |
| BR (2) | BR112014031322B1 (en) |
| CA (2) | CA2880611C (en) |
| DK (2) | DK2880072T3 (en) |
| ES (3) | ES2594877T3 (en) |
| MX (2) | MX345938B (en) |
| MY (2) | MY169025A (en) |
| PL (2) | PL2880072T3 (en) |
| SG (2) | SG11201500777QA (en) |
| SI (2) | SI2880072T1 (en) |
| WO (2) | WO2014020072A2 (en) |
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| CN108137838A (en) * | 2015-09-04 | 2018-06-08 | 吉瑞特(英国)有限公司 | Prepreg and the composite material production using prepreg |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SI2678368T1 (en) | 2011-02-23 | 2015-08-31 | Alzchem Ag | Novel curing agents for epoxy resins |
| US9499659B2 (en) * | 2012-08-02 | 2016-11-22 | Alzchem Ag | Liquid hardeners for hardening epoxide resins (I) |
| WO2015113931A1 (en) * | 2014-01-29 | 2015-08-06 | Alzchem Ag | Liquid curing composition for curing polymer resins (ii) |
| DE102014000992A1 (en) | 2014-01-29 | 2015-07-30 | Alzchem Ag | Liquid hardener composition for curing polymer resins (I) |
| DE102014000993A1 (en) | 2014-01-29 | 2015-07-30 | Alzchem Ag | Liquid hardener composition for curing polymer resins (II) |
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| CN108675679B (en) * | 2018-06-15 | 2021-06-01 | 武汉德立固材料股份有限公司 | Liquid curing agent for hardening and corrosion prevention of leak board and use method thereof |
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| IT201800010629A1 (en) | 2018-11-27 | 2020-05-27 | Microtex Composites S R L | PREPREG FOR AESTHETIC COMPONENTS WITH HIGH THERMAL RESISTANCE AND FREE OF DEFECTS SUCH AS STAINS AND DOTS AND THEIR PRODUCTION METHOD. |
| JP7235561B2 (en) * | 2019-03-28 | 2023-03-08 | 日鉄ケミカル＆マテリアル株式会社 | EPOXY RESIN COMPOSITION, FIBER REINFORCED COMPOSITE MATERIAL AND MOLDED PRODUCT |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2743015A1 (en) * | 1977-09-23 | 1979-04-05 | Lentia Gmbh | METHOD OF CURING EPOXY RESINS |
| CN1798787A (en) * | 2003-05-30 | 2006-07-05 | 底古萨股份公司 | Use of urea derivatives as accelerators for epoxy resins |
| CN101215453A (en) * | 2007-12-28 | 2008-07-09 | 中电电气集团有限公司 | Adhesive for middle-temperature solidifying epoxy pre-dipping material and preparation method thereof |
| CN101240154A (en) * | 2008-03-04 | 2008-08-13 | 上海回天化工新材料有限公司 | Single-component high peel strength epoxy resin adhesive and preparation method thereof |
| WO2009124998A2 (en) * | 2008-04-11 | 2009-10-15 | Basf Se | Hyperbranched polymers and oligomers comprising terminal amino groups as curing agents for epoxy resins |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6709961A (en) | 1966-07-19 | 1968-01-22 | ||
| BE755863A (en) * | 1969-09-09 | 1971-03-08 | Ciba Geigy | CURING COMPOSITIONS OF EPOXIDIZED RESINS |
| DE2122955B2 (en) * | 1971-05-10 | 1976-03-04 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Process for the preparation of epoxy polyadducts |
| JPS5341704B2 (en) * | 1972-07-12 | 1978-11-06 | ||
| DE2459752A1 (en) | 1974-12-18 | 1976-07-01 | Schering Ag | Epoxide polyadducts having increased pot life - from epoxides, cyanamide monomer and stabilisers |
| DE2642023C3 (en) | 1976-09-18 | 1980-12-18 | Skw Trostberg Ag, 8223 Trostberg | Process for stabilizing aqueous cyanamide solutions |
| JPS53125475A (en) * | 1977-04-08 | 1978-11-01 | Mitsubishi Rayon Co Ltd | Prepreg |
| AT351772B (en) | 1977-09-27 | 1979-08-10 | Chemie Linz Ag | METHOD OF CURING EPOXY RESINS WITH CYANAMIDE |
| JPS585925B2 (en) * | 1978-07-23 | 1983-02-02 | 東邦ベスロン株式会社 | Epoxy resin composition for carbon fiber prepreg |
| US4507445A (en) | 1982-10-12 | 1985-03-26 | Ciba-Geigy Corporation | Heat-curable epoxide resin compositions |
| JPS6069126A (en) | 1983-09-27 | 1985-04-19 | Toshiba Chem Corp | Thermosetting resin composition |
| DE3412086A1 (en) * | 1984-03-31 | 1985-10-10 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING STORAGE-STABLE CYANAMIDE SOLUTIONS IN POLYOLS, SINGLE-PHASE HOMOGENEOUS CYANAMIDE SOLUTIONS AND THEIR USE |
| US5429831A (en) | 1984-11-09 | 1995-07-04 | Hester Industries, Inc. | Marinated meat and poultry products having a glazed coating and method for producing such products |
| DE3510952A1 (en) * | 1985-03-26 | 1986-10-09 | Skw Trostberg Ag, 8223 Trostberg | HARDENER SOLUTION FOR EPOXY RESINS |
| JPH0699542B2 (en) | 1985-06-03 | 1994-12-07 | チバ−ガイギ− アクチエンゲゼルシヤフト | Hardener mixture for epoxy resin and method of use thereof |
| DE3682537D1 (en) | 1985-06-06 | 1992-01-02 | Ciba Geigy Ag | POLYEPOXIDES AND THEIR USE. |
| DE3540524A1 (en) | 1985-11-15 | 1987-05-27 | Bayer Ag | FUEL-CONTAINING INTUMESCENT MATERIALS BASED ON EPOXY RESIN |
| US4754003A (en) * | 1986-04-22 | 1988-06-28 | Ciba-Geigy Corporation | Phenol ethers containing epoxide groups |
| DE3714997A1 (en) * | 1987-05-06 | 1988-11-17 | Aeg Isolier Kunststoff | EPOXY RESIN FORMULATION WITH EXTREMELY SHORT CURING TIME |
| US5352831A (en) | 1987-09-02 | 1994-10-04 | Ciba-Geigy Corporation | Oligomeric cyanoguanidines |
| DE3815234A1 (en) * | 1988-05-05 | 1989-11-16 | Sueddeutsche Kalkstickstoff | ACCELERATORS FOR CYANAMIDE CONTAINING EPOXY HAIR |
| JPH0759626B2 (en) * | 1989-07-12 | 1995-06-28 | 日立化成工業株式会社 | Epoxy resin composition for printed wiring board |
| ES2071078T3 (en) | 1989-11-21 | 1995-06-16 | Ciba Geigy Ag | MIXTURES OF MATERIALS, HARDENABLE, BASED ON EPOXY RESIN, CONTAINING A LATENT HARDENER, AN AMINE AND A THYOL. |
| DE4026363A1 (en) | 1990-08-21 | 1992-03-12 | Sueddeutsche Kalkstickstoff | 1- (N'-CYANOGUANYL) DERIVATIVES OF N-CONTAINING FUENFRINGHETEROCYCLES |
| FR2686089B1 (en) | 1992-01-15 | 1995-07-13 | Brochier Sa | COMPOSITION BASED ON EPOXY RESIN AND APPLICATIONS, PARTICULARLY IN COMPOSITE STRUCTURES. |
| US5407977A (en) | 1993-04-20 | 1995-04-18 | The Dow Chemical Company | Solvent system |
| GB9315526D0 (en) | 1993-07-27 | 1993-09-08 | Dow Deutschland Inc | Solvent system |
| DE4342721A1 (en) | 1993-12-15 | 1995-06-22 | Hoechst Ag | Elastic epoxy resin hardener system |
| DE4410785A1 (en) | 1994-03-28 | 1995-10-05 | Hoechst Ag | Amine modified epoxy resin composition |
| US5620831A (en) | 1994-04-05 | 1997-04-15 | Taiyo Ink Manufacturing Co., Ltd. | Cyanoguanidine derivatives, and thermosetting or photocurable, thermosetting resin composition using the same |
| JP3851366B2 (en) | 1995-10-30 | 2006-11-29 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Photosensitive resin composition |
| JP4719976B2 (en) | 1999-03-11 | 2011-07-06 | 東レ株式会社 | Epoxy resin composition, epoxy resin composition for fiber reinforced composite material, and fiber reinforced composite material having the same |
| JP2000355630A (en) * | 1999-04-14 | 2000-12-26 | Toray Ind Inc | Member made from fiber-reinforced plastic |
| AU2003284676A1 (en) | 2002-12-02 | 2004-06-23 | Kyoeisha Chemical Co., Ltd. | Curable urethane resin composition |
| US20040147711A1 (en) | 2003-01-23 | 2004-07-29 | Christiansen Walter H. | Epoxy resin compositions, methods of preparing, and articles made therefrom |
| CN1513893A (en) | 2003-03-18 | 2004-07-21 | 上海回天化工新材料有限公司 | Epoxy resin lalent solidifying agent |
| DE102005057590A1 (en) | 2005-12-02 | 2007-06-06 | Degussa Ag | Use of 1- (N'-cyanoguanyl) derivatives of N-containing five-membered heterocycles as curing agents for epoxy resin compositions |
| DE102006012550A1 (en) | 2006-03-18 | 2007-09-20 | Degussa Gmbh | Use of a substituted guanidine compound and its salts or hydrates as a hardener for epoxy resins |
| GB0619401D0 (en) | 2006-10-02 | 2006-11-08 | Hexcel Composites Ltd | Composite materials with improved performance |
| DE502007002766D1 (en) * | 2007-11-14 | 2010-03-18 | Sika Technology Ag | Thermosetting epoxy resin composition containing non-aromatic ureas as accelerator |
| DE102009052061A1 (en) | 2009-11-05 | 2011-05-12 | Alzchem Trostberg Gmbh | Use of guanidine derivatives as curing accelerator for epoxy resins |
| SG185028A1 (en) * | 2010-04-30 | 2012-11-29 | Dow Global Technologies Llc | Phosphazene blocked azole compounds as latent catalysts for epoxy resins |
| DE102010020882A1 (en) | 2010-05-18 | 2011-11-24 | Alzchem Trostberg Gmbh | Semicarbazone for curing epoxy resins |
| EP2426160B1 (en) * | 2010-09-03 | 2014-01-15 | Sika Technology AG | Heat curable epoxy resin composition with water as foaming agent |
| SI2678368T1 (en) * | 2011-02-23 | 2015-08-31 | Alzchem Ag | Novel curing agents for epoxy resins |
| DE102011012079A1 (en) | 2011-02-23 | 2012-08-23 | Alzchem Ag | Liquid hardener useful e.g. for hardening of hardenable polymer resins, preferably epoxy resins, comprises cyanamide and at least one urea derivative |
| US9499659B2 (en) | 2012-08-02 | 2016-11-22 | Alzchem Ag | Liquid hardeners for hardening epoxide resins (I) |
-
2013
- 2013-07-31 US US14/407,232 patent/US9499659B2/en active Active
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-
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- 2018-05-09 JP JP2018090789A patent/JP2018123343A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2743015A1 (en) * | 1977-09-23 | 1979-04-05 | Lentia Gmbh | METHOD OF CURING EPOXY RESINS |
| CN1798787A (en) * | 2003-05-30 | 2006-07-05 | 底古萨股份公司 | Use of urea derivatives as accelerators for epoxy resins |
| CN101215453A (en) * | 2007-12-28 | 2008-07-09 | 中电电气集团有限公司 | Adhesive for middle-temperature solidifying epoxy pre-dipping material and preparation method thereof |
| CN101240154A (en) * | 2008-03-04 | 2008-08-13 | 上海回天化工新材料有限公司 | Single-component high peel strength epoxy resin adhesive and preparation method thereof |
| WO2009124998A2 (en) * | 2008-04-11 | 2009-10-15 | Basf Se | Hyperbranched polymers and oligomers comprising terminal amino groups as curing agents for epoxy resins |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137838A (en) * | 2015-09-04 | 2018-06-08 | 吉瑞特(英国)有限公司 | Prepreg and the composite material production using prepreg |
| US10913833B2 (en) | 2015-09-04 | 2021-02-09 | Gurit (Uk) Ltd. | Prepregs and production of composite material using prepregs |
| US11505642B2 (en) | 2015-09-04 | 2022-11-22 | Gurit (Uk) Ltd. | Prepregs and production of composite material using prepregs |
| CN106987095A (en) * | 2017-05-16 | 2017-07-28 | 广东博汇新材料科技股份有限公司 | High transparency epoxy resin composition for prepreg and preparation method thereof |
| CN110297392A (en) * | 2018-03-23 | 2019-10-01 | 株式会社田村制作所 | Photosensitive polymer combination |
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